Titanic-oxid concentrate and method for producing the same.



AUGU's'rE J. nossr AND LOUIS E.

UNITED STATES PATENT OFFICE.-

ons TO THE TITANIUM ALLoY A CORPORATION or MAINE.

BARToN, or NIAGARA FALLS, NEW YORK, 'AssIeN- MANUFACTURING COMPANY, or NEW YORK, N. Y.,

TITANIC-0X11) GONCENTRATE AND METHOD FOR PRODUdING- THE SAME.

No Drawing.

. oxid, as for:,example titaniferous iron ores.

.. stances on, industrial scales, whereby the re- The objects of our invention comprise prov1s1on of methods for treating such subsultin'g products shall contain higher percentages of titanic oxid than have any heretofore naturally, or artificially produced,

our said resulting titanic oxid product having also novel desirable characteristics, and being so producible more economically and readily than any other titanic oxid concentrates known to us.

Our method herein described as a comprehensive organized procedure comprises several steps which we believe to be individually novel and which are useful in modiportions" of the said in redients of the charge are preferably suc' "as,'determin'ed by analysis of the particular ore, or sub-'- stance, treated, to supply-sufficientfofsucha oxid of an alkali metal to combine Withe'ley ha fringchemifications of our said method which omit some of the entire series of steps herein described as constituting said procedure.

lVe attain the said objects of our invention preferably as follows :We first finely pulverize the ore, or substance, containing titanic oxid. and then melt it with admixed oxid of an alkali metal (preferably commerciali'caustic soda) and carbon, in some form, as, for example coke until the charge is. thoroughly melted and "iron oxids present reduced to elemental iron." Thereljative pro ments'and compounds presen cal affinity therefor, as fore uple'iv-ith'the titanic oxid to form--titana'te of soda (Na,TiO, and to supply 'suflicient carbon. to reduca the iron oxids present. But} n it er e de y; fi ejew ewe s Specification of Letters Patent.

Application filed November 29, '1912. Serial No. 733,942.

' actions.

prohibitoryf For example merely,in treatmg an are which analyzed Titanic oxid 52 Iron oxids' 4O 7 Silica 3 Alumina 4.

we successfully proportioned the charge as follows, viz

Ore 298 parts59. 6% Soda (70%)---- 172parts'-34=.3% Coke 30parts 6.0%

The melting of the charge is preferably conducted 'in an electric furnace, but it may of course be accomplished by any other desiredmeans capable of insuring a complete melt and reduction of iron oxid to elemental iron, as for example in an open hearth furnace heated by direct coke fire in a grate,

Y or indirectly by producer gas, such furnaces being of course lined with material sufiiciently refractory to resist the resulting re- VVe believe that, during the melt, the following reactions, among others, occur in the charge, viz: Oxid of sodium combines with .titanic oxid to form titanate of soda, thus readily brcakingup ilmen-ite molecules if any present. Oxids of iron present are reduced to elemental iron. any, remaining unreduced are maintained in ferrous state. Silica and alumina of the gangue combine with the oxid of sodium to form silicates and aluminates of soda. Care is taken-toregulate the duration and temperature of the said smelting operation so as to retainlin the resulting melt after its cooling, and homogeneously distributed therethrough, particles of elemental iron (usually in spongy form) resulting from the aforesaid reduction of the iron oxids; Said particles so located in intimate and uniformly distributed association with the titanium .compouuds of the melt are, by reason of their" said distribution and condition, onabled to produce, at a later hereinafter described stage, results more rapidly and pen .fectlythan through mere extraneous additions of iron or other metal. The melt being Withdrawn from the furnace in anv con- Patented Au 11, 19M.

Oxids of iron, if-

venient manner is allowed to cool and then well crushed say to 80 mesh sieve. It is then repeatedly and thorough] lixiviated in heated, preferably boiling, water, until substan- 5 tially all the therein contained titanate of soda has been decomposed into titanic oxid and'caustic soda. The soda thus set free, together with any excess soda and said silicates and alumi'nates, being soluble, dissolve, and are thus removed from the undissolved residue of the melt with the Water of lixiviation. It will be noted that the, soda lye resulting from said lixiviation can be evaporated to a cake of soda useful in treating as 5 aforeasid the next charge of ore. In our practice we have thus repeatedly recuperated approximately 85%, or even more, of the soda employed, the which constitutes an important economy in the practice of our present method. What still remains of'the melt after its aforesaid treatment may be ex-. pected to be substantially free from excess of soda, from silica and alumina and their compounds, and from most of the iron oxids, but to retain substantially all of the titanic oxid, and also, therewith intimately and homogeneously associated throughout, particles of elemental iron, and said small quantities of unreduced iron oxids, these latter being insoluble in water, together with some slight remainders of gangue, including magnesia, the said'o-res containing not to exceed traces of lime. It will be noted that the said unreduced iron oxids being as aforesaid in ferrous state are more soluble in the hereafter mentioned acid bath than if in ferric state. This last'mentioned remainder of the melt we then subject, and preferably while still moist, to the action of a heated, preferably boiling, bat-h containing sulfuric acid.. We prefer'to proportion the sulfuric acid in quantity sufiicient to insure the greatest pos- 'sible solution of the titanic oxid present, say in practice a bath containing from 50% to 60% of sulfuric acid and the volume of th bath, relatively to the melt therein treated? being, of course, proportioned as by usual good practice, '5. e. great enough to insure the aforesaid solution without undue excess' of sulfuric acid. It will be noted that contact of the melt with our said bath results in imparting to the latter a blue or violet, color. This is due to formation in the bath of titanous sulfate attributable to the reducing action of nascent hydrogen evolved from reaction of the aforesaid elemental iron particles present with sulfuric acid. Our said blue or violet bath is then withdrawn from its insoluble residues, as by decanting, being thus substantially freed from any solid impurities, and contaminations by unreduced and undissolved substances; but containing ferrous and titanous sulfates. We'have discovered that in consequence of the novel con- V ditions' created'in our said bath by 9 .1? af resaid procedure we are enabled, by-suitable precipitation to derive therefrom a novel substance, 71. e. a basic titanic sulfate, '5. e. a chemical combination of titanic sulfate with ydrated titanic acid. \Ve have'discovered that if to our said bath be added a'very small amount, preferably about one half of one per cent.'in volume of nitric acid and boiling it, precipitation of our said novel compound will be greatly accelerated, the concentration of our bath, at the time of such L addition, being preferably reduced but not so far as to result in precipitation of previously known titanic acid products such as metatitanic acid. It will be understood that the nitric acid when thus added in such relatively minute quantity is incapable of oxidizing, unless negligibly, the titanous sulfate present to titanic sulfate as per the equation 3Ti (SO +2HNO ,+3H. ,SO,:

6Ti S0 2+2NO+4=H20 and therefore the nitric acid does not itself act as the required precipitant of our process, but it seems merely to accelerate, or pro-- mote, the precipitation otherwise caused by the oxygen of the atmosphere. Precipitation occursin our boilin bath independently of our addition 0% the nitric acid Which, as employed by us, we believe to'act merely ,as a catalytic agent greatly stimulating and accelerating the oxidation of the 'titanous sulfate as required for its precipis tation as a basic sulfate. Repeatedtests have demonstrated that precipitation of our composition by boiling only, requires from one and a half to two hours, whereas by addition of the said minute quantity of nitric acid to the boiling solution the precipita- 1 5 tion occurs to the same extent in less than one half of that time. We have repeatedly produced our said novel composition, z'. e.

the said precipitate, by our above described method, and we find, by analysis, that, 1 practice, its constituents vary between certain definite limits substantially as follows I Titanic oxid 70 to 8 Sulfuric anhydrid 5 to 10% Combined water 15-to 20% I "Ve have claimed, in a herewith contempo-raneously filed application for patent, our saidvcomposition as noveland as our in- 2 vention- Our said novel composition, being the precipitate derived from our saidbath as aforesaid, we then calcine, the resulting product containing a higher percentage ofpure titanic oxid than hitherto, obtainable in nature, .or by any industi ially practicable method of production, and also possessing other novel, superior. and advantageous characteristics which render it exceptionally desirable for many-uses. vOur titanic'oxid tanic oxid products,

rutile,

analysis of our titanic mg from calcinatlon of product 'thusp'rod'uced'is characterized 'as being in the form-of an exceedingly pure and' fine, amorphous powder, nearly white or sometimes of a lig t yellow .or bufl' shade, attributable probably to traces, or unimportant amounts of iron or its compounds; also as being, as compared to previous .tior concentrates, of a non-granular very soft and smooth texture, and of lower specific gravity, say 3.77 or not to exceed 3.80 as compared to the specific gravity 4.18 to 4.25 of pulverized natural or the specific gravity 3199 of titanic oxid produced by calcination of what is known as meta-titanic, or ortho-titanic, acids. Such previously obtained titanic acids, for example those termed ortho titanic acids, derived by aidgof alka1i-'pre-' cipitation of acid. solutions being character ized as very hard, horny andde'nse' masses; also the titanic oxids, such as meta-titanic acids, derived from precipitationfrom acidsolutions of titanium, such as titanium ch10 rid and titanium sulfate, diluted with water; and boiled, being, when dried and calcined in the form of coarse,

oxid powder resultour said'precipitatc has disclosed as its constituents Alumina 9 7 Titanic oxid 98. 45%

'ercenta es, ire. above 99% of pure titanic oxid.

n will be understood this, as Use-a the aforesaid ox'ids'ofan-alkaline niet'a'l', caustic potash may be employed in lieu of caustic soda, and in the same way as above de scribed, but'- we prefer; the latter,;not' only because of its" comparatively lower cost, but also because of its superior efliciencyunder the eondi'tionsmentioned;

What we claim" as newan'd desire to sec' l'e' by Letters Patent is the following,

1 The" methodof obtaining titanic oxid I (T10 fr'oma substance containing it and iron oxid, which comprises smelting said substan e together .Ihetal in} presence of a reducing agentso'as to produce titanato' of saidalkali metaland elementafiron in the resulting" melt, lixivia'ting in heated'water such nielt com tainingelement'al iron,- subjecting the thereafter rema'ini containing sill arid-acid,

' pl ecip of titanium; and

the resulting precipitate.

a. The method bf'obtaining'titanic oxid" {TiQQ from a substancecoutaaning: tunnel gritty powder; All

with oxid of an alkali n melt to'th'e" action of a "bath ting-out of compounds withdrawing'andcalcining iron oxidg "wliich comprises smelting said substance to,'gethe"r with caustic soda in presence or a reducing agent so as to produce tit'an'ate of'soda and elementaliron in the resulting melt, lixiviating in heated water such' melt containing elemental iron, subjecting-the'thereafter remaining melt to the action, of" abath containing sulfuric acid, precipitating out of said bath the therein contained compounds of titanium, and withdrawing and calcining the resulting precipitate.

3. The method of obtaining titanic oxid (TiO from a substance containing it and iron oxid, which comprises smelting said substance together with oxid of an alkali metal in presence of a reducing agent so as to produce't-it'anate of said alkali metal and elemental iron in the resulting melt, lixiviating in heated Water such melt containing elemental iron, subjecting the thereafter remaining melt to the action of a bath containing sulfuric acid, boiling said bath With addition of nitric acid and withdrawing and calcining the resulting precipitate.

4. The method of obtaining titanic oxid ('I iO) from a substance containing it and boiling'said bath-with addition of nitric acid and withdrawing'and calcining the resulting precipitate.

5. Inobtaining'titanicloxid (TiO from a substance containing-it and iron oxid, the steps which comprise smelting said substance together with oxid of an alkali metal in presence of a reducing agent until iron oxid is reduced to elemental iron, lixiviating in heated Water the melt containing ele- I'ne'ntal iron and subjecting the undis'solved rcsid'u'es to the action of a bath containing sulfuric acid suflicient to dissolve therein compounds of titanium.

6., In obtaining titanic oxid (TiO from in. substancecontaining it and iron oxid, the steps which comprise" smeltingsaid substa'nce' together with caustic soda in pres ence of a reducing agent until iron oxid is reduc'ed to elemental iron, lixiviating in heated water the melt containing elemental ironand subjectingthe undis'solved residues "tothe action of a; bath contaming-sulfuric j ac'i'd su'fiicien't to dissolve therein compounds of titanium;

7. "In obtaining tita" a substance containi =steps'u%hich comprisesmelting said sub stance together' rfith caustic: sodain presence For carbon until oxid its reduced to alemental iron, 1ixiviating in heated water the melt containing elemental iron and subject-" ing the undissolved residues to the action of a' bath containing sulfuric acid sufiicient to; dissolve therein compounds of titanium.

8. In obtaining titanic oxid (TiO from a substance containing it and iron oxid, the steps which comprise smelting said substance together with oxid of an alkali metal in presence of carbon until iron oxid is reduced to elemental iron, lixiviating in heated water the. melt containing elemental iron and subjecting the undissolved residues to the action of a bath containing sulfuric acid sufiicient to dissolve therein compounds of titanium.

9. In obtaining titanic oxid (TiO from a substance containing it and iron oxid,

' the steps which comprise smelting said subthe steps which comprise smelting said sub-' oxid is reduced to elemental iron,

tity insuflicient to oxidize all tanous sulfate to titanic sulfate,

stance together with oxid of an alkali metal in presence of a reducing. agent until iron lixiviating in heated water the melt containing elementaliron, subjecting the undissolved residues to the action of a bath containing sulfuric acid sufficient to dissolve therein compounds of titanium, boiling said bath with nitric insufficient to oxidize all calcining the resulting precipitate.

10. In obtaining titanic oxid (TiO,) from a substance containin it and iron oxid,

stance together with causticsoda in presence of a reducing agent until iron oxid is reduced to elemental iron,lixiviating in heated water the melt containing elemental iron,

subjecting the undissolved residues to theaction of a bath containing sulfuric acid sufficient to dissolve therein compounds of titanium, boiling saidbath .with nitric acid in quantity insutlicient to oxidize all therein tita'nous sulfate to titanicsulfate, and calcining the resulting precipitate. 4

11. In obtaining titanic oxid (TiO,) from a substance containin it and iron oxid, the steps which comprise smelting said substance together with caustic soda in presence of carbon until iron oxid is reduced to elemental iron, lixiviating in heated water the melt containing elemental iron, subjecting the undissolved residues to the act-ion of a bath containing sulfuric acid sufiicient to,

dissolve therein compounds] of titanium, boiling said bath with nitric acid in quantherein tiand calcining the resulting precipitate.

12. In obtaining titanic oxid (TiO,) from a substance containing it and. iron oxid, the steps'iwhich comprise smelting said' substancettogether' with .ox-id of an alkali metal in presence of carbon until ,iron oxid is reduced to -elemental iron,ligriviating in heated water the melt containing elementpl/ iron bath -'to dissolve therein compounds of titanium,

subjecting the undissolved residues to the action of a bath containing sulfuric acid sufiicient to dissolve therein compounds of titanium, boiling said bath with nitric acid in quantity insufficient to oxidize all therein titanous sulfate to titanic sulfate, andcalcining the resulting precipitate.

13. In obtaining titanic oxid (TiO from a substance -coutaining it and iron oxid, the steps which comprise smelting said substance in presence of a reducing agent, dissloving in part the resulting melt in a bath containing sulfuric acid suflicient to dissolve therein compounds of titanium, boiling said bath with-nitric acid in quantity insuflicient to oxidize all therein titanous sulfate to titanic sulfate, and calcining the resulting precipitate.

14. In the treatment of a bath containing titanous sulfate in solution, the step which consists in boiling said bath with nitric acid in proportion such as to promote precipitation therein of basic titanic sulfate.

15. In obtaining titanic oxid (TiO from a substance containing it and iron oxid the steps which comprise smelting said sub stance together with oxid of an alkali metal in presence of'a reducing-agent, subjecting the resulting melt to; thefaction of a bath containing sulfuric acid suflicient to dissolve therein compounds of titanium, precipitating out of said bath the resulting compounds of titanium, and calcining the resulting precipitate.

16. In obtaining titanic oxid (TiO,) from a substance containing it and iron oxid the steps which comprise smelting said substance together with oxid of an alkali metal in presence of a reducing agent, and subjecting the resulting melt to the action of a boiling containing both sulfuric acid sufficient and also nitric acid in proportion such as to promote precipitation therein of basic titanic sulfate.

17. The process of obtaining titanic oxid (TiO from'a substance containing it and iron oxid, which comprises smelting said substance. together with, oxid of an alkali metal in presence of a reducing agent, subjecting the resulting melt to the action of a 50% to 60% sulfuricacid bath of volume proportioned to insure solution of the therein compounds of titanium, adding thereto nitric acid not to exceed 1% ofits volume, reducing its concentration, and boilingit' H 18. As a new article a titanic oxid concentrate characterized as being a calcined product in the form of a fine, amorphous, non-granular, soft, smooth, powder, "nearly white or light yellow, or light buff, in color, as containing a preponderance of titanic oxidand also iron and other substances not to exoeed 2%.r,

taining a preponderance oftitanic oxid and also iron and other substances not to exceed 2%.-

21. As a new article a titanieoxid concen trate characterized as being a calcined product, of specific gravity 3.77 to 3.80, in the form of a fine, amorphous, non-granular,

soft, smooth, powder, nearly white or light yellow, or light bull, in color, as containing titanic oxid not less than 98%, and also iron and other substances not to exceed 2%. v

AUGUSTE J. ROSSI.

' LOUIS E. BARTON.

Witnesses:

WALTER D. EDMONDS, PHILIP G. Prom 

